CN1096472C - Method for polymerization of alpha-olefins - Google Patents

Method for polymerization of alpha-olefins Download PDF

Info

Publication number
CN1096472C
CN1096472C CN98109844A CN98109844A CN1096472C CN 1096472 C CN1096472 C CN 1096472C CN 98109844 A CN98109844 A CN 98109844A CN 98109844 A CN98109844 A CN 98109844A CN 1096472 C CN1096472 C CN 1096472C
Authority
CN
China
Prior art keywords
polymerization
olefin
magnesium
compound
alpha
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN98109844A
Other languages
Chinese (zh)
Other versions
CN1199053A (en
Inventor
鲁基洙
金一燮
杨春柄
朴允锡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hanwha Total Petrochemicals Co Ltd
Original Assignee
Samsung General Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung General Chemicals Co Ltd filed Critical Samsung General Chemicals Co Ltd
Publication of CN1199053A publication Critical patent/CN1199053A/en
Application granted granted Critical
Publication of CN1096472C publication Critical patent/CN1096472C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44

Abstract

A method for polymerization or copolymerization of alpha -olefin, characterized in that the polymerization is performed using a solid complex titanium catalyst comprising magnesium, a halogen-containing titanium compound, and internal electron donors; organometallic compounds of metals belonging to Groups I and III on the periodic table of elements; and, as external electron donors, a mixture of three or more kinds of organic silicon compounds, from which homopolyolefins having MFR less than 5, MFR in the range from 5 to 20, and MFR greater than 20 are polymerized under the same polymerization conditions. By use of the present invention it is possible to produce an olefin polymer with high stereoregularity, broad molecular weight distribution, and good fluidity, at high rates of yield.

Description

The polymerization process of alpha-olefin
Invention field
The present invention relates to a kind of production method of olefin polymer or multipolymer of high directionality, when the polymerization of the alpha-olefin that is used to have three or more carbon atoms or copolymerization, this method productivity height, molecular weight distribution that simultaneously can controlling polymers.
Background technology
Usually, use MgCl 2The olefin polymer of the Catalyst Production of carrier band has narrow molecular weight distributions.Up to the present, many trials that add wide molecular weight distribution had been done, so that adding the flow characteristics of improving man-hour by the product of this Catalyst Production.For this reason, widely used a kind of method is, uses the multiple aggregation reactor to make the polymkeric substance that different molecular weight distributes earlier, mixes then, and still, its shortcoming is, needs many times and workload, and, often find that product is very inhomogeneous.In nearest report, the Mitsui Petrochemical of Japan has advised a kind of method (the open 93-665 of Korean Patent), wherein by using two kinds of specific electron donor(ED) productions to have olefin polymer than wide molecular weight distribution, thus, under identical polymerizing condition, respectively the polymerization melting index than (MFR) greater than 31.6 homopolymerization polyolefine.Yet in the case, activity of such catalysts is fallen too lowly and can not be used in industry, and, be not only its molecular weight distribution and be difficult to control, and, the reactivity of the hydrogen of catalyzer and controlling polymers molecular weight distribution is so low, to such an extent as to propose many restrictions when its process operation.
Simultaneously, known use solid complexing titanium catalyst is produced many other methods of high directionality polymkeric substance or multipolymer, as the polymerization or the copolymerization catalyst that contain more than the alpha-olefin of three carbon atoms, described catalyzer contains magnesium and electron donor(ED), (for example also contains titanium and halogen, the open communique 73-16986 and 16987 of Japanese Patent, German Patent discloses 2153520,2230672, and 2230728,2230752 and 2553104).
These document illustrations the production method of the use of special catalyst component of mixture and these catalyzer.As everyone knows, along with the different mixtures of component, the difference combination of Recipe, with the different combinations of these conditions, these characteristics of catalyzer that contain solid complexing titanium are different with catalyzer.Therefore, be difficult to foretell which type of effect the catalyzer of producing can obtain under given condition.Often produce catalyzer with non-constant effect.The such fact of also normal appearance, even under suitable condition, produce catalyzer, if do not use suitable external electrical to give body, can not demonstrate fully the characteristic as the directional property of activity of such catalysts or polymkeric substance.
The solid complexing titanium catalyst that contains magnesium, titanium and halogen does not make an exception.In the polymerization or copolymerization that contain more than the alpha-olefin of three carbon atoms, the catalyzer of in the presence of hydrogen, forming by titanium and the organometallic compound that belongs to period of element Table I family to IV family metal with use, if use by using metallic aluminium, the promotor that the titanous chloride that hydrogen or organo-aluminium compound reduction titanium tetrachloride obtain is formed, and the electron donor(ED) of the generation of known limitation amorphous copolymer, be difficult to expect ground, this effect will become with used electron donor(ED).The received reason of this reason is, electron donor(ED) is not only inert additwe, on the contrary, they with magnesium and titanium compound electronics and space combine, therefore changed the structure of solid complex catalyst substantially.
The Dow Corning of the U.S. (USP5175332 and European patent disclose 602922), the Mitsui Petrochemical of Japan (open 92-2488 of Korean Patent and 93-665, USP4990479, European patent discloses 350170, Canadian Patent 1040379), and many European manufacturerss of knowing have developed some novel methods, compare with existing method, by using certain silicon compound, can high yield generate polymkeric substance.
Summary of the invention
Therefore, the inventor also keeps successfully having finished the present invention after the method for activity of such catalysts through the molecular weight distribution of the controlling polymers that studies for a long period of time simultaneously.The directional property that keeps activity of such catalysts and polymkeric substance, the H-H reaction of the molecular weight distribution of controlling polymers and increase catalyzer simultaneously, and obtain bigger benefit in operation, now become possibility.In the present invention, use more than three kinds of silicoorganic compound and give body polymerization or copolymerization alpha-olefin, thus as external electrical, under identical polymerizing condition, be lower than 5,5 to 20 and by using various external electrical to have MFR respectively for body, polymerization greater than 20 homopolymerization polyolefine.
The invention provides a kind of production method of olefin polymer or multipolymer of high directionality, when the production that is used for having more than the alpha-olefinic polymer of three carbon atoms or multipolymer, this method can be controlled the molecular weight distribution of olefin polymer or multipolymer simultaneously.
Specific purposes of the present invention provide the production method of a kind of polypropylene and propylene copolymer, this polymkeric substance is applicable to the production film, and this film can be easy to heat seal, is transparent and has non-stick property, this polymkeric substance has shock resistance, but mobile and low temperature heat seal.Detailed Description Of The Invention
The method of alpha-olefine polymerizing of the present invention or copolymerization is used: (a) a kind of solid complexing titanium catalyst, and it contains magnesium, halogen-containing titanium compound and give the ester polycarboxylate of body as internal electron; (b) belong to the organometallic compound of period of element Table I family and III family metal; (c) external electrical is given body, and it comprises three kinds or more kinds of silicoorganic compound, and thus, under identical polymerizing condition, polymerization has MFR (melt flow rate (MFR)) respectively and is lower than 5, MFR in 5 to 20 scopes and MFR greater than 20 homopolymerization polyolefine.
The solid complexing titanium catalyst (a) that is used for alpha-olefine polymerizing or copolymerization in the present invention contains magnesium, and halogen-containing titanium compound is as basal component with as the ester polycarboxylate of internal electron to body.
Compare with existing titanium catalyst, the solid complexing titanium catalyst of Shi Yonging has fabulous catalytic activity level in the present invention, and can produce the polymkeric substance with wide molecular weight distribution and high directionality.It has halogen/titanium mol ratio greater than about 4, and it still is a kind of solid complex, when at room temperature washing in hexane, does not in fact have titanium compound to separate.Do not know the chemical structure of this solid complex, still, the atom of supposition magnesium and the atom of titanium are fixedly connected by halogen.In the present invention in the preferred embodiment of the solid complexing titanium of Shi Yonging, halogen/titanium mol ratio is preferably greater than about 8 greater than about 5; Magnesium/titanium mol ratio surpasses about 3, more preferably about 5 to about 50, and electron donor(ED)/titanium mol ratio about 0.2 is to about 6, preferred about 0.4 to about 3, even more preferably from about 0.8 to about 2.Specific surface area is greater than 10m 2/ g is preferably greater than about 50m 2/ g is more preferably greater than about 100m 2/ g.The X-ray spectrum of solid complexing titanium catalyst preferably shows and the irrelevant amorphous feature of raw material magnesium, perhaps, compares the more unbodied characteristic of demonstration with the conventional magnesium dihalide on the market.
Can produce the solid complexing titanium catalyst that uses in the present invention by many methods.As the method for broad practice, the irreducibility magnesium compound contacts with halogen-containing titanium compound and if desired, handles its product with electron donor(ED), and these methods can be used entirely in the present invention.Disclose 2230672,2504036 at German Patent, 2553104 and 2605922; The open communique 51-28189 of Japanese Patent has showed the part in these methods among 51-136625 and the 52-87486.Described the ordinary method of producing solid complexing titanium compound in the open communique 79-40239 of Japanese Patent, this method begins and contains electron donor(ED) with the liquid titanium compound form from the liquid magnesium solution.
For the irreducibility magnesium compound, can adopt magnesium halide, as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; The alkoxyl group magnesium halide is as methoxyl group chlorination magnesium, oxyethyl group magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octyloxy magnesium chloride; The aryloxy magnesium halide is as phenoxy group magnesium chloride and methylphenoxy magnesium chloride; Alkoxyl magnesium, as magnesium ethylate, isopropoxy magnesium, butoxy magnesium and octyloxy magnesium; Aryloxy magnesium is as phenoxy group magnesium and dimethyl phenoxy magnesium; The magnesium salts of acid is as lauroyl magnesium and Magnesium Stearate.In complex compound, magnesium compound can use with the mixture of other metal or other metal.Also can use the mixture of two or more magnesium compounds.Preferred magnesium compound is hydrogenous magnesium compound, is more preferably magnesium chloride, and alkoxy-magnesium chloride most preferably contains C 1-C 14The alkoxy-magnesium chloride of alkoxyl group and aryloxymagnesium chloride also preferably contain C 6-C 20The aryloxymagnesium chloride of aryloxy.
Generally can be by the concise and to the point above-mentioned magnesium compound of listing of general formula representative, still, because different production methods, occurring other sometimes is not relevant especially magnesium compound.In the case, it has been generally acknowledged that they are mixtures of these compounds.For example, according to different reactants or different level of response, at halogenated silanes, phosphorus pentachloride or thionyl chloride exist down, obtain by magnesium metal and alcohol or phenol reaction, perhaps the heat of solution by Grignard reagent obtains, and perhaps all is considered to the mixture of all cpds by those compounds that use hydroxyl, carbonyl ester group, ether or other group dissolving Grignard reagent to obtain; In the present invention, such compound also suits.
In the present invention, mainly use irreducibility liquid magnesium compound or the magnesium compound solution in hydrocarbon solvent.The hydrocarbon solvent of those magnesium compounds that on solubilized, provide exist or not in the presence of, can be by irreducibility magnesium compound and at least a or multiple alcohol of listing above that is selected from, organic carboxyl acid, aldehyde, such liquefied compound is produced in the electron donor(ED) reaction of amine or its mixture.
The hydrocarbon solvent of Shi Yonging comprises for this purpose, for example, aliphatic hydrocrbon, as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbon, as pentamethylene, methylcyclopentane, hexanaphthene, and methylcyclohexane; Aromatic hydrocarbons, as benzene, toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, and cymene; And halohydrocarbon, as ethylene dichloride, propylene dichloride, Ethylene Dichloride, trieline, tetracol phenixin, and chlorobenzene.
Can mix by simple, or by heating in the mixing process, or by being selected from alcohol, aldehyde, amine, the electron donor(ED) of carboxylic acid or its mixture exists down and mixes, or even mixes with other electron donor(ED)s and they are heated the magnesium compound solution of producing hydrocarbon solvent by these mixtures.Yet, can change this production method according to the type of magnesium and solution.When dissolving contains Hydromagnesia compound in hydrocarbon solution, use alcohol as electron donor(ED), the amount and the ratio of alcohol can change according to the amount and the kind of magnesium compound and hydrocarbon solvent, but, every mole of magnesium compound wishes to use at least 0.5 mol of alcohol, preferred 1.0 to 20 moles, more preferably from about 2.0 to about 10 moles.
Have under the situation of at least 6 carbon atoms at the alcohol that uses, if every mole of halogen-containing magnesium compound uses at least 0.5 mole, or preferred at least 1.0 mol of alcohol, then can only use a spot of alcohol just can dissolve halogen contained compound and can obtain to have highly active catalyst component.Contain 5 or the alcohol of carbon atom still less if use, the total amount that one mole of magnesium compound uses alcohol is at least about 15 moles, and, compare with using alcohol in the aforesaid method, so the catalyst component of producing will have lower activity.Simultaneously, if use aromatic hydrocarbons as hydrocarbon solvent, do not consider the type of alcohol, one mole of magnesium compound uses about 20 moles of alcohol, preferred about 1.5 moles to 12 moles, can dissolve hydrogenous magnesium compound.
Preferably in hydrocarbon solvent, carry out the reaction of halogen-containing magnesium compound and alcohol.According to the kind of magnesium compound and alcohol, in room temperature or higher temperature, for example, at about 30 ℃ to about 200 ℃, or more preferably from about 60 ℃ to about 150 ℃, the reaction times is about 15 minutes to about 5 hours, more preferably about 30 minutes to about 3 hours, carries out this reaction.
The alcohol that is used as electron donor(ED) in preparation liquid magnesium compound comprises fatty alcohol, as the 2-methyl amyl alcohol, and 2-ethylpentanol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol, tetradecanol, undecylenic alcohol, oleyl alcohol and Stearyl alcohol; Alicyclic ring alcohol is as hexalin and methyl-cyclohexanol; And aromatic alcohol, as benzylalcohol, xylyl alcohol, isopropylidene benzylalcohol, α-Jia Jibianchun, α, alpha-alpha-dimethyl benzylalcohol, they all have at least 6 or preferred 6-20 carbon atom.For containing 5 or the alcohol of carbon atom still less, can use methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol and methyl carbitol and similar alcohol.
Utilize silicon tetrahalogen once more, alkyl halide silicon, four tin halide, alkyl tin halide, hydrohalogenation tin, titanium tetrahalide and analogue crystallize into spherical solid with the magnesium compound of the liquid form of above-mentioned production.Recrystallize into the silicon compound that uses in the spherical solid at the liquid magnesium compound, tin compound, or the amount of titanium compound is different with situation.1 mole of magnesium compound can use 0.1 mole to 20 moles, and preferred 0.1 mole to 10 moles, more preferably 0.2 mole to 2 moles.The shape and size of magnesium carrier also will become with reaction conditions.When two kinds of compound, they must keep under the suitable quite low temperature so that they do not solidify in reaction process, then with product slowly heating to produce solid.The recrystallization temperature scope of liquid magnesium compound is-70 ℃ to about 200 ℃ approximately.Usually, for obtaining particle or spherical products, in the hybrid technique process, preferably avoid high temperature.Yet if temperature of reaction is too low, solid product will not precipitate, and therefore, preferably carry out this reaction at about 20 ℃ to about 150 ℃.
Internal electron to body in the presence of, so magnesium compound and the liquid titanium compound that obtains reacts, and obtains solid complexing titanium catalyst thus.Be preferably as follows the tetravalent titanium compound of general formula: Ti (OR) with the titanium compound of the liquid form of magnesium compound reaction mX 4-m(wherein R is an alkyl, and X is a halogen atom, and m is the number of 0-4).The R representative contains the alkyl of 1 to 10 carbon atom.Can use various titanium compounds, titanium tetrahalide, for example, TiCl 4, TiBr 4, and TiI 4Alkoxyl group three halogenated titaniums, for example, Ti (OCH 3) Cl 3, Ti (OC 2H 5) Cl 3, Ti (OC 4H 9) Cl 3, Ti (OC 2H 5) Br 3, and Ti (O (i-C 2H 5)) Br 3Alkoxyl group dihalide titanium, for example, Ti (OCH 3) 2Cl 2, Ti (OC 2H 5) 2Cl 2, Ti (OC 4H 9) 2Cl 2, and Ti (OC 2H 5) 2Br 2The alkoxyl group halogenated titanium, for example, Ti (OCH 3) 3Cl, Ti (OC 2H 5) 3Cl, Ti (OC 4H 9) 3Cl, and Ti (OC 2H 5) 3Br; And four titan-alkoxide mixtures, for example, Ti (OCH 3) 4, Ti (OC 2H 5) 4, and Ti (OC 4H 9) 4
With at least 1 mole of per 1 mole of irreducibility magnesium compound, preferred about 3 moles to about 200 moles, more preferably from about 5 moles of extremely about 100 moles ratios are used titanium compound.Preferably mixed magnesium compound and liquid titanium compound, slowly intensification then at low temperatures.For example, two kinds of compounds contact to avoid rapid reaction at-70 ℃ to about 50 ℃ earlier, slowly are warmed up to about 50 ℃ to about 150 ℃ then, carry out time enough so that make reaction, after this, with used hydrocarbon washed product in the polyreaction, up to can not measuring separative titanium.Method can be produced fabulous solid complexing titanium catalyst thus.
The internal electron that uses in producing solid complexing titanium catalyst can be to contain positro to give body to body usually, for example, and water, alcohol, phenol, aldehyde, carboxylic acid, ester, ether, and acid amides; And nitrogenous electron donor(ED), for example, ammonia, amine, nitrile, and isocyanic ester; The alcohol that particularly contains 1 to 18 carbon atom, for example, methyl alcohol, ethanol, propyl alcohol, amylalcohol, hexanol, octanol, dodecanol, Stearyl alcohol, benzylalcohol, phenylethyl alcohol, cumic alcohol, and Isobutyl Benzyl Carbinol; Contain 6 to 15 carbon atoms and the ketone that can contain low alkyl group, for example, phenol, cresols, dimethylbenzene, ethyl phenol, propyl phenoxy, cumylphenol, and naphthols; The aldehyde that contains 2 to 15 carbon atoms, for example, acetaldehyde, propionic aldehyde, octanal, phenyl aldehyde, toluic aldehyde, and naphthaldehyde; The organic acid acetic that contains 2 to 18 carbon atoms, for example, methyl-formiate, methyl acetate, ethyl acetate, vinyl-acetic ester, propyl acetate, octyl acetate, hexalin acetate, ethyl propionate, methyl-butyrate, Valeric acid ethylester, chloromethyl acetate, acetate dichloro ethyl ester, methyl methacrylate, butenoic acid ethyl, the cyclohexane carboxylic acid ethyl ester, phenol benzoate, peruscabin, toluic acid methyl esters, ethyl toluate, toluic acid pentyl ester, ethylamino benzonitrile acetoacetic ester, p-Methoxybenzoic acid methyl ester, ethyl anisate, ethoxy benzonitrile acetoacetic ester, the g-butyrolactone, s-valerolactone, cumalin, 2-benzo [c] furanone, hexalin acetate, ethyl propionate, methyl-butyrate, methyl valerate, chloracetic acid methyl esters, the dichloro-ethyl acetate, methyl methacrylate, naphthenic acid (cycloate) ethyl ester, phenol benzoate, toluic acid methyl esters, ethyl toluate, propyl benzoate, butyl benzoate, phenylformic acid cyclohexyl, the toluic acid pentyl ester, carbonic acid methylene radical ester and carbonic acid ethylidene ester; The halogenated compound that contains 2 to 15 carbon atoms, for example, Acetyl Chloride 98Min., benzyl chloride, chlorotoluene manthanoate, chloro fennel acid esters; Acid amides, for example, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran (THF), phenylmethylether, and diphenyl ether; Amine, for example, methylamine, ethamine, diethylamine, tributylamine, piperidines, tribenzyl amine, aniline, pyridine, spirits of rosin (pynoline), and tetramethylene-diamine; Nitrile, for example, acetonitrile, benzonitrile, and Bian Jiqing; And the aluminium, silicon, tin compound and the analogue that in its molecule, contain above-mentioned functional group; In addition, in the present invention, use to produce to have the directional property of improvement and the alpha-olefinic polymer of high yield more with some electron donor(ED) catalyst for reaction.In the present invention, be used to produce the preferred internal electron of solid complexing titanium catalyst to body especially monoethylene glycol (MEG), glycol ether (DEG), triglycol (TEG), polyoxyethylene glycol (PEG), the ester derivative of single propylene glycol (MPG) and dipropylene glycol, for example, acetic ester, propionic ester, just and isobutyrate, benzoic ether, toluic acid ester etc., benzoic ether is the monoethylene glycol mono benzoate, the monoethylene glycol dibenzoate, diglycol monotertiary benzoic ether, diethylene glycol dibenzoate, the diglycol monotertiary benzoic ether, triethylene glycol dibenzoate, single propylene glycol mono benzoate and other ester.These electron donor(ED)s can use with two or more form of mixtures, particularly preferably are the ester of aryl.Beginning does not always need these electron donor(ED)s, and they also can be introduced in the process of producing solid complexing titanium catalyst, and they also can be used as to the additive of other compounds or with the form of complex compound and use.Internal electron changes for the amount of body with the need.Per 1 mole of magnesium compound can be about 0.01 to about 10 moles, preferred about 0.01 to about 5 moles, or more preferably 0.05 to about 1 mole.
Is granular or globular by using the solid catalyst that generates by the polymkeric substance that slurry polymerization obtains, and has fabulous directional property, high-bulk-density and good flowability.
Above-mentioned solid complexing titanium catalyst can be used for the polymerization of following alkene effectively, as ethene, and propylene, 1-butylene or 4-methyl-1-pentene.This catalyzer is specially adapted to contain the polymerization of the alpha-olefin of three or more carbon atoms, and the copolymerization of these alkene contains the copolymerization of the alpha-olefin that is lower than 10 molar ethylenes, and the copolymerization that is applicable to the alpha-olefin that contains conjugation and non-conjugated diene.
The organometallic compound of Shi Yonging (b) especially comprises trialkylaluminium in the method for the invention, for example, and triethyl aluminum and tri-butyl aluminum; Alkenyl aluminium, triisophrenyl aluminium for example, part alkoxylated alkyl group aluminium, for example, the dialkyl group aluminum alkoxide is as diethylaluminum ethoxide and dibutyl butoxy aluminium; Alkyl sesquialter aluminum halide and ethylaluminum dichloride are as ethyl sesquialter aluminum ethoxide and butyl sesquialter aluminum ethoxide; Alkyl dihalide aluminium is as propyl group al dichloride and butyl aluminum dibromide; Partially halogenated aluminium, for example, dialkyl group aluminum hydride and ethyl oxyethyl group aluminum chloride are as ADEH and dibutyl aluminum hydride; And part alkoxylate and alkyl aluminum halide, as butyl butoxy aluminum chloride and ethyl oxyethyl group aluminum bromide.
In the present invention, in polymerization process, use more than three kinds of such silicoorganic compound and give body, to improve the directional property of the polymkeric substance of being produced as external electrical.The silicoorganic compound of Shi Yonging ethyl triethoxysilane particularly in the present invention, the n-propyl triethoxyl silane, tertiary butyl triethoxyl silane, vinyltriethoxysilane, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, biconjugate tolyl dimethoxy silane, p-methylphenyl methyl dimethoxysilane, dicyclopentyl dimethoxyl silane, the dicyclohexyl methoxy silane, cyclohexyl methyl dimethoxy silane, 2-norbornane triethoxyl silane, 2-norbornane methyl dimethoxysilane, the phenylbenzene diethoxy silane, or other silane compound, perhaps, can also use and contain cyclopentyl, cyclopentenyl, the organometallic compound of cyclopentadienyl and derivative thereof.
Can in liquid phase or gas phase, carry out polyreaction, still even and tap density is high for the polymer particle size of using Catalyst Production of the present invention, be more suitable for adopting vapour phase polymerization.
In liquid polymerization, can use inert solvent such as hexane, heptane and kerosene also can be with alkene itself as reaction mediums as reaction medium.Under the liquid polymerization situation, the preferred concentration of solid complexing titanium catalyst (a) is per 1 liter of total overall reaction thing and solvent, and in titanium atom, about 0.001mmol is to about 5mmol, and more preferably from about 0.001mmol is to about 0.5mmol.Under the situation of vapour phase polymerization, per 1 liter of total overall reaction thing and solvent, also in titanium atom, about 0.001mmol is to about 5mmol, and more preferably from about 0.001mmol is to about 1.0mmol, also 0.01mmol about 0.5mmol extremely more preferably from about.
Per 1 mole of titanium atom in solid complexing titanium catalyst (a), the ratio of the aluminium atom of organometallic compound component (b) is about 1mol to 2000mol, preferably about 5mol is to about 500mol.The aluminium atom of per 1 molar constituent (b), in Siliciumatom, external electrical give the ratio of body component (c) be about 0.001mol to about 10mol, or preferably about 0.01mol about 2mol extremely, more preferably from about 0.05mol about 1mol extremely.
Use the polyreaction of catalyzer of the present invention with the method identical with the ordinary method of using Ziegler-type catalyst.It should be noted that under anaerobic and anhydrous condition and carry out this reaction.Be about 20 ℃ to about 200 ℃ in temperature preferably, more preferably from about 50 ℃ to about 180 ℃ is about normal pressure to 100 normal atmosphere at pressure, carries out this olefinic polyreaction under preferred about 2 normal atmosphere to 50 normal atmosphere.Can by intermittently or semi-batch or continuous mode carry out this reaction, and can two of different condition goes on foot or multistep be carried out this reaction to have.
Embodiment
Below, illustrate in greater detail embodiment of the present invention by embodiment and comparative example.
Embodiment 1 (production of solid titanium catalyst component (a))
With 5g (0.053mol) MgCl 2Join in 1 liter of glass reactor with the 50mol n-decane and under nitrogen atmosphere, stirred 1 hour, then, in this mixture, slowly add 25ml (0.16mol) 2-ethyl-1-hexanol.Solution is heated to 120 ℃ and allow its reaction 2 hours, then, adds 2ml diisobutyl phthalate reaction 1 hour, obtain homogeneous phase solution.Reduce the temperature to room temperature, drip 30mlTiCl 4, temperature of reaction is raised to 90 ℃, allows solution reaction 2 hours, generates solid carrier.Add 2.0g (0.007mol) dibenzoic acid monoethylene glycol ester as second electron donor(ED), make solution 90 ℃ of reactions 1 hour.Reclaim solid matter, in refined hexane, wash, up in washings, no longer including isolating titanium tetrachloride.In the carrier of acquisition like this, add the purified heptane, with 1 hour to wherein dripping 40molTiCl 4, be heated 100 ℃, reacted 2 hours.The solid catalyst that washing so generates in refined hexane, up in hexane, no longer including isolating titanium component, then, dry and under nitrogen atmosphere, store for future use.This solid complexing titanium catalyst (a) contains 2.5% (weight) titanium atom.(polymerization)
Clean the high-pressure reactor of 2 liter capacities with propylene, the 38mg catalyzer in the glass phial (measure with titanium atom, titanium component is 0.02mmol) is put into reactor, the reactor and fill nitrogen three times of finding time.Then, with 10mmol triethyl aluminum and 0.1mmol dicyclopentyl dimethoxyl silane, 0.8mmol cyclohexyl methyl dimethoxy silane, 0.1mmol vinyl Ethoxysilane, be added to together in the reactor with the 1000ml normal hexane, wherein the back three is that external electrical is given body.After hexane adds, add 100Nml (0 ℃, 1 normal atmosphere) hydrogen, temperature is raised to 70 ℃.Propylene gas is added in the polymerization reactor (2 liters of Parr reactors, 4521 types) through MFC (streams controller), wherein, propylene has been removed its water and oxygen in advance in oxygen scavenqer and molecular sieve trap.When propylene at total pressure 7kg/cm 2When reaching the gas/liquid balance, smash phial in the reactor, allow the reaction beginning thus with agitator.Reaction continues 1 hour, then, allows the high-pressure contents cool to room temperature, adds 10ml ethanol to finish activity of such catalysts.Reclaim the polymkeric substance that generates thus, drying is about 6 hours in 50 ℃ of vacuum drying ovens, obtains the polypropylene of 140.6g powder type thus.In this polymkeric substance, after extracting in boiling n-heptane, the residuum ratio that stays is 98.0%, and tap density is 0.41g/ml, and MFR 6.3, and molecular weight distribution (Mw/Mn) 6.9.Embodiment 2
To carry out polymerization with embodiment 1 identical method, the different 0.15mmol dicyclopentyl dimethoxyl silanes that are to use, 0.7mmol cyclohexyl methyl dimethoxy silane and 0.15mmol vinyltriethoxysilane are given body as external electrical, the results are shown in the table 1.
Embodiment 3
To carry out polymerization with embodiment 1 identical method, the different 0.2mmol dicyclopentyl dimethoxyl silanes that are to use, 0.6mmol cyclohexyl methyl dimethoxy silane and 0.2mmol vinyltriethoxysilane are given body as external electrical, the results are shown in the table 1.
Embodiment 4
To carry out polymerization with embodiment 1 identical method, different is to use the 0.25mmol dicyclopentyl dimethoxyl silane, 0.5mmol cyclohexyl methyl dimethoxy silane, give body with the 0.25mmol vinyltriethoxysilane as external electrical, the results are shown in the table 1.
Embodiment 5
To carry out polymerization with embodiment 1 identical method, the different 0.45mmol dicyclopentyl dimethoxyl silanes that are to use, 0.1mmol cyclohexyl methyl dimethoxy silane and 0.45mmol vinyltriethoxysilane are given body as external electrical, the results are shown in the table 1.
Embodiment 6
To carry out polymerization with embodiment 1 identical method, the different 0.25mmol dicyclopentyl dimethoxyl silanes that are to use, 0.5mmol cyclohexyl methyl dimethoxy silane, give body with the 0.25mmol vinyltriethoxysilane as external electrical, and add 200Nml hydrogen, the results are shown in the table 1.
Embodiment 7
To carry out polymerization with embodiment 1 identical method, the different 0.25mmol dicyclopentyl dimethoxyl silanes that are to use, 0.5mmol cyclohexyl methyl dimethoxy silane, give body with the 0.25mmol vinyltriethoxysilane as external electrical, and add 400Nml hydrogen, the results are shown in the table 1.Comparative example 1
To carry out polymerization with embodiment 1 identical method, the different 1.0mmol dicyclopentyl dimethoxyl silanes that are to use are given body as external electrical, the results are shown in the table 1.Comparative example 2
To carry out polymerization with embodiment 1 identical method, the different 1.0mmol cyclohexyl methyl dimethoxy silane that are to use are given body as external electrical, the results are shown in the table 1.Comparative example 3
To carry out polymerization with embodiment 1 identical method, the different 1.0mmol vinyltriethoxysilanes that are to use are given body as external electrical, the results are shown in the table 1.Comparative example 4
To carry out polymerization with embodiment 1 identical method, different be to use 0.5mmol dicyclopentyl dimethoxyl silane and 0.5mmol vinyltriethoxysilanes are given body as external electrical, the results are shown in the table 1.Comparative example 5
To carry out polymerization with embodiment 1 identical method, different be to use 0.5mmol dicyclopentyl dimethoxyl silane and 0.5mmol vinyltriethoxysilanes are given body as external electrical, and add 200Nml hydrogen, the results are shown in the table 1.Comparative example 6
To carry out polymerization with embodiment 1 identical method, different be to use 0.5mmol dicyclopentyl dimethoxyl silane and 0.5mmol vinyltriethoxysilanes are given body as external electrical, and add 400Nml hydrogen, the results are shown in the table 1.
Table 1: polymerization result
Embodiment Polymerizing condition The result
External electrical is given body (1) External electrical is given body (2) External electrical is given body (3) H 2(Nm l) Active (Kg-PP/g-catalyzer, hour) Residuum behind the normal heptane extraction Melting index (g/10 minute) Tap density (g/ml) (Mw /Mn)
Kind mmol Kind mm ol Kind mm ol
Embodiment 1 DCPD MS 0.10 CHM DMS 0.8 VT ES 0.10 100 3.7 98.0 6.3 0.41 6.9
Embodiment 2 DCPD MS 0.15 CHM DMS 0.7 VT ES 0.15 100 3.7 98.3 5.7 0.39 7.1
Embodiment 3 DCPD MS 0.20 CHM DMS 0.6 VT ES 0.20 100 3.6 98.5 4.7 0.40 7.5
Embodiment 4 DCPD MS 0.25 CHM DMS 0.5 VT ES 0.25 100 3.2 98.0 8.0 0.40 7.6
Embodiment 5 DCPD MS 0.45 CHM DMS 0.1 VT ES 0.45 100 3.0 98.1 3.5 0.38 8.0
Embodiment 6 DCPD MS 0.25 CHM DMS 0.5 VT ES 0.25 200 3.0 97.6 10.7 0.40 7.5
Embodiment 7 DCPD MS 0.25 CHM DMS 0.5 VT ES 0.25 400 3.7 98.0 19.5 0.40 7.4
Comparative example 1 DCPD MS 1.0 -- -- -- -- 100 4.3 98.3 3.7 0.39 5.8
Comparative example 2 CHM DMS 1.0 -- -- -- -- 100 3.5 96.3 10.1 0.37 5.9
Comparative example 3 VTES 1.0 -- -- -- -- 100 0.6 95.4 39.4 0.35 5.7
Comparative example 4 DCPD MS 0.5 VTE S 0.5 -- -- 100 3.1 97.2 2.9 0.32 8.0
Cohesive force 5 DCPD MS 0.5 VTE S 0.5 -- -- 200 3.5 98.0 4.7 0.34 8.0
Comparative example 6 DCPD MS 0.5 VTE S 0.5 -- -- 400 3.2 98.0 13.0 0.34 7.5
* DCPDMS: dicyclopentyl dimethoxyl silane CHMDMS: cyclohexyl methyl dimethoxy silane VTES: vinyltriethoxysilane

Claims (5)

1. the method for polymerization or copolymerization alpha-olefin, the catalyst system that this method is used comprises: (a) a kind of solid complexing titanium catalyst, it contains magnesium, and halogen-containing titanium compound and at least a internal electron are given body; (b) belong to the organometallic compound of period of element Table I family and III family metal; (c) external electrical is given body, and it comprises the mixture of three kinds or more kinds of silicoorganic compound, and thus, under identical polymerizing condition, polymerization has MFR respectively and is lower than 5, MFR in 5 to 20 scopes and MFR greater than 20 homopolymerization polyolefine.
2. according to the polymerization of claim 1 or the method for copolymerization alpha-olefin, wherein, described inner electron donor is for containing oxygen electron donor or nitrogenous electron donor.
3. according to the polymerization of claim 1 or 2 or the method for copolymerization alpha-olefin, wherein, described internal electron is selected from monoethylene glycol to body, glycol ether, triglycol, polyoxyethylene glycol, the ester of single propylene glycol and dipropylene glycol.
4. according to the polymerization of claim 1 or 2 or the method for copolymerization alpha-olefin, wherein, described organometallic compound (b) is a trialkylaluminium.
5. according to the polymerization of claim 1 or 2 or the method for copolymerization alpha-olefin, wherein, in described polymerization, use external electrical to give body, described external electrical is a dicyclopentyl dimethoxyl silane to body, cyclohexyl methyl dimethoxy silane, vinyltriethoxysilane, and wherein said alpha-olefin is a propylene.
CN98109844A 1997-05-08 1998-05-08 Method for polymerization of alpha-olefins Expired - Lifetime CN1096472C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1019970017650A KR100334167B1 (en) 1997-05-08 1997-05-08 Process for polymerizing alpha-olefin
KR17650/97 1997-05-08

Publications (2)

Publication Number Publication Date
CN1199053A CN1199053A (en) 1998-11-18
CN1096472C true CN1096472C (en) 2002-12-18

Family

ID=19505170

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98109844A Expired - Lifetime CN1096472C (en) 1997-05-08 1998-05-08 Method for polymerization of alpha-olefins

Country Status (3)

Country Link
US (1) US6066702A (en)
KR (1) KR100334167B1 (en)
CN (1) CN1096472C (en)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100334167B1 (en) * 1997-05-08 2002-11-22 삼성종합화학주식회사 Process for polymerizing alpha-olefin
KR100546499B1 (en) * 1999-05-27 2006-01-26 삼성토탈 주식회사 A catalyst for ethylene homo- and co-polymerization
ATE276281T1 (en) 1999-10-23 2004-10-15 Samsung General Chemicals Co IMPROVED CATALYST FOR OLEFIN HOMO- AND CO-POLYMERIZATION
KR100361224B1 (en) * 1999-12-01 2002-11-29 삼성종합화학주식회사 Method for preparing catalyst for ethylene homo- and co-polymerization
KR20010057153A (en) * 1999-12-18 2001-07-04 유현식 Propylene polymerization and copolymerization method
KR100377288B1 (en) * 2000-06-12 2003-03-26 삼성종합화학주식회사 A method for propylene polymerization or copolymerization
KR100359932B1 (en) 2000-06-15 2002-11-07 삼성종합화학주식회사 A catalyst for ethylene homo- and copolymerization
KR100389477B1 (en) * 2000-11-09 2003-06-27 삼성종합화학주식회사 A method for producing ethylene homo- and co-polymer
US6566294B2 (en) * 2000-12-21 2003-05-20 Exxonmobil Chemical Patents Inc. Multi-donor catalyst system for the polymerization of olefins
KR100421553B1 (en) 2000-12-27 2004-03-09 삼성아토피나주식회사 A polymerization method of alpha-olefins
KR100496776B1 (en) 2001-06-21 2005-06-22 삼성토탈 주식회사 Catalyst for polymerization and copolymerization of ethylene
KR100530794B1 (en) 2001-06-21 2005-11-23 삼성토탈 주식회사 Catalyst for polymerization and copolymerization of ethylene
KR100530795B1 (en) * 2001-12-26 2005-11-23 삼성토탈 주식회사 A method for ethylene homo- and copolymerization
CN1169845C (en) * 2002-02-07 2004-10-06 中国石油化工股份有限公司 Solid catalyst component for olefine polymerization, catalyst with the component and its application
WO2003106512A2 (en) * 2002-06-14 2003-12-24 Union Carbide Chemicals & Plastics Technology Corporation ; Catalyst composition and polymerization process using mixtures of selectivity control agents
EP1641835B1 (en) * 2003-06-24 2010-01-06 Union Carbide Chemicals & Plastics Technology LLC Catalyst composition and polymerization process using mixture of silane electron donors
KR101114748B1 (en) 2003-09-23 2012-03-05 다우 글로벌 테크놀로지스 엘엘씨 Self limiting catalyst composition and propylene polymerization process
CN1856513A (en) * 2003-09-23 2006-11-01 联合碳化化学及塑料技术公司 Self limiting catalyst composition and propylene polymerization process
CZ2006179A3 (en) * 2003-09-23 2007-01-31 Dow Global Technologies Inc. Catalyst composition with monocarboxylic acid ester internal donor and propylene polymerization process
JP2007505983A (en) * 2003-09-23 2007-03-15 ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション Catalyst composition having mixed selectivity control agent and propylene polymerization method
US7381779B2 (en) * 2003-09-23 2008-06-03 Dow Global Technologies Inc Self limiting catalyst composition with dicarboxylic acid ester internal donor and propylene polymerization process
KR101157697B1 (en) * 2008-09-03 2012-06-20 삼성토탈 주식회사 Method for producing propylene polymer having a high melt-flowability
ES2727405T3 (en) * 2011-12-30 2019-10-16 Borealis Ag Preparation of phthalate free ZN PP catalysts
US10696756B2 (en) 2015-08-07 2020-06-30 Sabic Global Technologies B.V. Process for the polymerization of olefins
CN108137718B (en) 2015-08-07 2020-07-14 Sabic环球技术有限责任公司 Process for the polymerization of olefins
CN108174605B (en) * 2015-08-07 2021-03-26 Sabic环球技术有限责任公司 Process for the polymerization of olefins

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045400A (en) * 1989-03-02 1990-09-19 三井石油化学工业株式会社 The catalyzer that the polymerization process of alkene and polymerizing olefins are used
CN1062147A (en) * 1990-11-27 1992-06-24 阿普里尔公司 Propylene polymerization promotor based on silane and monoether
US5407883A (en) * 1992-04-14 1995-04-18 Showa Denko K.K. Catalyst for polymerization of olefin and process for the preparation of olefin polymer
US5436213A (en) * 1991-10-02 1995-07-25 Borealis Holding A/S Procatalyst composition containing substituted maleic or fumaric acid esters as an electron donor for olefin polymerization

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4156063A (en) * 1971-06-25 1979-05-22 Montecanti Edison, S.p.A. Process for the stereoregular polymerization of alpha olefins
US4226963A (en) * 1971-06-25 1980-10-07 Montedison S.P.A. Process for the stereoregular polymerization of alpha-olephins
US4187196A (en) * 1971-06-25 1980-02-05 Montedison S.P.A. Process for the stereoregular polymerization of alpha-olefins
US4107413A (en) * 1971-06-25 1978-08-15 Montedison S.P.A. Process for the stereoregular polymerization of alpha olefins
US4107414A (en) * 1971-06-25 1978-08-15 Montecatini Edison S.P.A. Process for the stereoregular polymerization of alpha olefins
NL160286C (en) * 1971-06-25
US4071674A (en) * 1972-09-14 1978-01-31 Mitsui Petrochemical Industries Ltd. Process for polymerization or copolymerization of olefin and catalyst compositions used therefor
US4071672A (en) * 1972-11-10 1978-01-31 Mitsui Petrochemical Industries Ltd. Process for polymerizing or copolymerizing olefins
US4157435A (en) * 1974-08-10 1979-06-05 Mitsui Petrochemical Industries, Ltd. Process for preparing highly stereoregular polyolefins and catalyst used therefor
JPS565404B2 (en) * 1975-02-14 1981-02-04
US4076942A (en) * 1975-10-01 1978-02-28 Merck & Co., Inc. Crystalline dipilocarpinium pamoate
US4069169A (en) * 1975-11-24 1978-01-17 Mitsui Petrochemical Industries Ltd. Process for preparation of catalyst component supported on high performance carrier
GB1603724A (en) * 1977-05-25 1981-11-25 Montedison Spa Components and catalysts for the polymerisation of alpha-olefins
IT1114822B (en) * 1977-07-04 1986-01-27 Montedison Spa COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS
IT1098272B (en) * 1978-08-22 1985-09-07 Montedison Spa COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS
JPS6037804B2 (en) * 1979-04-11 1985-08-28 三井化学株式会社 Method for manufacturing carrier for olefin polymerization catalyst
JPS56811A (en) * 1979-06-18 1981-01-07 Mitsui Petrochem Ind Ltd Preparation of olefin polymer or copolymer
JPS5883006A (en) * 1981-11-13 1983-05-18 Mitsui Petrochem Ind Ltd Polymerization of olefin
JPS5930803A (en) * 1982-08-11 1984-02-18 Nippon Oil Co Ltd Preparation of polyolefin
JPS60115603A (en) * 1983-11-29 1985-06-22 Toa Nenryo Kogyo Kk Polymerization of olefin
US4988656A (en) * 1984-03-23 1991-01-29 Amoco Corporation Olefin polymerization catalyst
US5013702A (en) * 1984-03-23 1991-05-07 Amoco Corporation Olefin polymerization catalyst
US4866022A (en) * 1984-03-23 1989-09-12 Amoco Corporation Olefin polymerization catalyst
JPS62267305A (en) * 1986-05-15 1987-11-20 Sumitomo Chem Co Ltd Production of olefinic polymer
JPS6354004A (en) * 1986-08-25 1988-03-08 Fujitsu Ltd Preamplifier
US4912074A (en) * 1988-01-15 1990-03-27 Mobil Oil Corporation Catalyst composition for preparing high density or medium density olefin polymers
EP0350170B2 (en) * 1988-06-17 2001-09-12 Mitsui Chemicals, Inc. Process for polymerising olefins and polymerisation catalyst therefor
US5134104A (en) * 1988-06-28 1992-07-28 Sumitomo Chemical Company, Limited Liquid catalyst component, catalyst system containing said component and process for producing ethylene-α-olefin copolymer using said catalyst system
IT1227259B (en) * 1988-09-30 1991-03-28 Himont Inc CATALYSTS FOR THE POLYMERIZATION OF OLEFINE.
JP2732478B2 (en) * 1989-03-02 1998-03-30 三井化学株式会社 Olefin polymerization method
US4946816A (en) * 1989-08-21 1990-08-07 Amoco Corporation Morphology-controlled olefin polymerization catalyst
DE69111354T2 (en) * 1990-04-18 1995-12-21 Mitsui Petrochemical Ind HOT MELT ADHESIVE.
US5081090A (en) * 1990-07-23 1992-01-14 Amoco Corporation Dry olefin polymerization catalyst
US5124297A (en) * 1990-12-07 1992-06-23 Amoco Corporation Olefin polymerization and copolymerization catalyst
US5182245A (en) * 1991-06-26 1993-01-26 Amoco Corporation Olefin polymerization and copolymerization catalyst
US5175332A (en) * 1991-12-16 1992-12-29 Dow Corning Corporation Cycloalkoxysilanes
JP3280477B2 (en) * 1992-08-31 2002-05-13 三井化学株式会社 Method for preparing solid titanium catalyst component for olefin polymerization
JPH06107730A (en) * 1992-09-29 1994-04-19 Tonen Corp Production of propylene copolymer
JPH06107731A (en) * 1992-09-29 1994-04-19 Tonen Corp Production of propylene copolymer
TW300235B (en) * 1992-12-04 1997-03-11 Mitsui Petroleum Chemicals Ind
EP0602922B1 (en) * 1992-12-14 1998-01-14 Dow Corning Corporation Method for producing dicycloalkylsubstituted silanes
EP0606125B1 (en) * 1993-01-08 1997-05-21 Shell Internationale Researchmaatschappij B.V. Use of titanium and zirconium compounds as homogeneous catalyst and novel titanium and zirconium compounds
EP0717053B1 (en) * 1994-11-25 2001-03-14 Japan Polyolefins Co., Ltd. Catalyst for olefin polymerization and process for producing polyolefin using the same
US5502128A (en) * 1994-12-12 1996-03-26 University Of Massachusetts Group 4 metal amidinate catalysts and addition polymerization process using same
KR100334167B1 (en) * 1997-05-08 2002-11-22 삼성종합화학주식회사 Process for polymerizing alpha-olefin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045400A (en) * 1989-03-02 1990-09-19 三井石油化学工业株式会社 The catalyzer that the polymerization process of alkene and polymerizing olefins are used
CN1062147A (en) * 1990-11-27 1992-06-24 阿普里尔公司 Propylene polymerization promotor based on silane and monoether
US5436213A (en) * 1991-10-02 1995-07-25 Borealis Holding A/S Procatalyst composition containing substituted maleic or fumaric acid esters as an electron donor for olefin polymerization
US5407883A (en) * 1992-04-14 1995-04-18 Showa Denko K.K. Catalyst for polymerization of olefin and process for the preparation of olefin polymer

Also Published As

Publication number Publication date
CN1199053A (en) 1998-11-18
KR19980082629A (en) 1998-12-05
KR100334167B1 (en) 2002-11-22
US6066702A (en) 2000-05-23

Similar Documents

Publication Publication Date Title
CN1096472C (en) Method for polymerization of alpha-olefins
RU2024303C1 (en) Method for production of catalytic system for (co)polymerization of olefins
CN100535023C (en) High activity and good hydrogen response ziegler-natta polyethylene catalyst
EP2206731B1 (en) Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method
CN1220708C (en) Process for alpha-olefine homopolymerization and co-polymerization
EP0926119A1 (en) Dialkoxybenzene electron donors
CN1189487C (en) A method for producing ethylene homo-and co-polymer
JP3549417B2 (en) Novel electron donor-containing composition
JPS6345404B2 (en)
CA1311741C (en) Preparation of olefin polymerization catalyst component
CN1856512A (en) Self limiting catalyst composition and propylene polymerization process
CN1271092C (en) Method of homo- or co-polymerization of dollar g(a)-olefin
JPS633007A (en) Production of polyolefin
CN1373777A (en) Catalyst for ethylene homo- and co-polymerization
CN1207312C (en) Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same
CN1220706C (en) Method for producing homo-and co-polymers of ethylene
CN1230451C (en) Catalyst for olefin polymerization and method of olefin polymerization using same
CN1478102A (en) Method for producing homo-and co-polymers of ethylene
CN100339399C (en) Method of polymerization and copolymerization of ethylene
JPH06145269A (en) Production of propylene block copolymer
JPH06100639A (en) Production of propylene block copolymer
CN1107682C (en) alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer
KR100218048B1 (en) Alpha-olefin polymerization catalyst and method for polymerizing alpha-olefin using the same
JPH07107083B2 (en) Method for producing propylene elastomer
JP3443849B2 (en) Method for producing propylene block copolymer

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: SAMSUNG ATOFINA CO., LTD.

Free format text: FORMER OWNER: SAMSUNG GENERAL CHEMICALS CO., LTD.

Effective date: 20031210

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20031210

Patentee after: Samsung General Chemicals Co

Patentee before: Samsung General Chemicals Co., Ltd.

C56 Change in the name or address of the patentee

Owner name: SAMSUNG ATOFINA CO., LTD.

Free format text: FORMER NAME: SAMSUNG GENERAL CHEMICALS CO

CP01 Change in the name or title of a patent holder

Address after: Chungnam, South Korea

Patentee after: Samsung Atofina Co., Ltd.

Address before: Chungnam, South Korea

Patentee before: Samsung General Chemicals Co

C56 Change in the name or address of the patentee
CP01 Change in the name or title of a patent holder

Address after: Chungnam, South Korea

Patentee after: SAMSUNG TOTAL PETROCHEMICALS

Address before: Chungnam, South Korea

Patentee before: Samsung Atofina Co., Ltd.

CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20021218